Manufacture of chlorhydrins



e Patented Oct. 1940 -Beamen- Roselle, N. J., `assignors` l Alcohol Co. o

invention-relates to processes of making chlorhydrins and relates particularly to a processv of producingchlorhydrins from gaseous mixtures containing. a'nqoleiine and saturated hydrocarbons L f with a minimum loss to'side reactions.

olenes, such as ethylene,A propylene and butylene', are thin 7mobilev liquids., more or lessV soluble in water. lWhen dry and pure, they have boilingV lo points` higher than that vof water, butin thev presence of water their boiling points are below 100 C. Olene chlorides and chlorhydrins may both or either be formed, depending upon the Aamount of water 'present during theV reaction. In the presence of relatively large bodiesvof water, chlorhydrins are .generally formed, but due to the presence of the Lsaid water, substantial L amounts of chlorhydrinsare mechanicallycar-z lried over when a gas containingVv relatively small portions of olenes is used as the starting ma-v terial'for preparing thechlorhydrins.

An object of vthis invention is to provide va method in whichV relatively dilute oleilne solutions are so treated that substantially all of the olene is recovered as Va chlorhydrin. This and other objects of the invention will be more clearI 1y understood on reading the following description with reference to the drawing. o. A tower designated by numeral l is partly iilled with water to the level 2. Into thisV tower is passed chlorine gas throughzinlet4 3 and distributing'cup ,4. Throughpipe 5 and distributing cup `6 is passed a hydrocarbon gas :containing from 10 to 50% or more of oleiines. Other suitable means of distributing the two gases in the lower partV of tower lv may be used. A bottom outlet 'l is provided to remove the vaqueous-solution of the product formedby reactingthe chlorine and hydrocarbon gas. Thisppevl is provided with 40 a valve 8. The levelyoi' the aqueous solution in:

tower l -is regulated by the opening Aor Vclosing f of valves which is operz'ttively connected lwitlri and actuated by float 9*'.

cally carries over some of the chlorhydrins and is passed into a packed V.tower Il. -Into thi'sfj., v packed tower water is passed through'pipe I2(v which water is previously cooled by passing throughexchanger I 3,'said exchanger ,I3 being provided with an inlet I4 and outlet lforfa cooling solution, such as brine. The water is The chiorhydrlns produced from the'gaseous Ythe iso-oleiines. yethylene chlorhydrim propylene and butylene.

. herent novelty inthe invention as broadly asthe I cooled suiiiciently so that, after passing in countercurrent .to the igas passing upwardly in thev :packed tower Il -it will absorbthechlorhydrins and ,leave the tower rll at :a .temperature from being removedv from'the'system through pipe l1. -By means of-this process, substantially all of the olefine injthe hydrocarbon mixture is con- Avertedtoreaction products; the residual spent hydrocarbon gasleaving the system Ythrough pipe 10 `|1,--being free fof reactants and Veffecting acom- 1 plete recoveryofy reaction products.v lThe temperatures are controlledandL maintained at 10 to y80" C.. in"tower I, depending on the oleflne concentration vand product desired. By the ciry1| y culation of the water through the system, a concentration of hydrochloricacid in tower I is also maintainedat allow degreeand, therefore, sub- Y stantially no /olene chlorides arehformed. This is a closed system and reaction is carried out in l0k towerl freeof any substantial illumination.. If desired, the lmixture of hydrocarbon gases which had beenv prepared 'by rcracking or ksubjecting .petroleum oils to 1temperatures of 400 to 900 C.

are flrstfmctionated to remove the higher boil- 25 j ing constituents and thenl treated with sulfuric acid of about- -70% concentration to' remove If desired, to ,prepare pure may-be first removed by contacting the gas with f 30 -98% sulfuric acid at suitable temperatures of between '.15 and 40. C. and then using the residual gas according to this process.

- 'The invention is not to be limited to the'spee cic embodiments nor to any theories advanced $5' as to the operation or the invention,v but in the appendedrclaims it is intended vtoclaim all lnmixture of. gaseous-hydrocarbons containing oleo o .1 iines and. parafns, .whichl comprises? passing a The olenes, on reacting with the chlorine in the presenceV of water, form chlorh'ydrina The* said chlorhydrlns form an emulsion in the waterl and a substantial quantity Vof foam. The spent ,V1 gas, in passing from tower l to pipe I0,1mechani mixture ofwolefl'nes and paraflinl hydrocarbonsv washing:y vthe spentl gasA withfwater cooled to af temperature not over 10 C.,v conducting the wash V'rivaliser with `the chlor'lnfdrins"m1-solutionl .to thev first saidj body" of water where `-it is contacted 50 ywith'chlorine and olefinesand continuously s epl aratingan'gaqueous solution of chlorhydrins.

2.r The process of makingV chlorhydrins, ywhich rvcomprises passing chlorine yand a gaseous mixture' of olene and paramn hydrocarbons in concur- 55 rent iiow through a body of water, passing the spent gas in countercurrent ow through water which is cooled to a temperature not over 10 C., passing the cooled water continuously into the rst said body of water and continuously withdrawing from said body of water an aqueous lsolution oi! chlorhydrins.

3. The process of making chlorhydrins, which comprises contacting a gaseous mixture of oleiines and Aparaiiin hydrocarbons with sulfuric acid .or 6070% concentration at a temperature within the range of between 15 and 40 C., then passing the hydrocarbons through a body of water concurrently with chlorine gas, passing the spent gas in countercurrent flow to water cooled to a temperature not over 10 C., passing the cooled water in countercurrent ow to the chlo-v rine and the said hydrocarbons and separating an aqueous` solution of chlorhydrins.

4. The process of making ethylene chlorhydrin, which comprises contacting a gaseous mixture of olefines and paraffin hydrocarbons with sulfuric acid of 8098% concentration at a ternperature within the range of 15 to 40 C., then passing the hydrocarbons through a body of water concurrently with chlorine gas, passing the spent gas in countercurrent iiow to water cooled to a temperature notv over 10 C., passing the cooled water in countercurrent ow to the chlorine and the said hydrocarbons and separating an aqueous solution of ethylene chlorhydrin.

5. The process of making chlorhydrins, which comprises contacting olenes and chlorine in the presence of water at a temperature not above 200 C., washing the spent gas with water cooled to a temperature not over 10 C., conducting the wash water with chlorhydrins in solution to contact with chlorine andolene and continuously separating an aqueous solution o! chlorhydrins.

6. The process of making chlorhydrins from a mixture of gaseous hydrocarbons containing oleiins and paraiilns, which comprises contactingja'mixture of olefin and paraffin hydrocarbons with chlorine in the presence of a body of water at a temperature not above 80 C., continuously adding Water cooled to a temperature not over 10 C. which has been used to absorb en'- trained chlorhydrins from the spent gas, to said body of water, and continuously separating an aqueous solution of chlorhydrins.

7. The process of making chlorhydrins from a mixture of gaseous hydrocarbons containing oleiins and paraffins, which comprises thestep of Aadding to an aqueous solution in which the chlorine and mixture of olefin and parafiln hydrocarbons are contacted at a' temperature not above 80C., a stream of water cooled to a temperature not over 10. C. which has been used to absorb entrained chlorhydrins Irom the spentv gas,v and continuously separating an aqueous so lution of chlorhydrins.

CHARLES A. COHEN. CLAYTON M. BEAMER. 

